Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
  • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
  • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring

Definitions

• the present invention relates to certain new 5-benzofuranyl esters which have been found to possess physiological activity, particularly plant physiological activity, to their preparation and to agricultural and other compositions containing the same. These compounds may be used as herbicides and as plant growth regulants. The compounds may also be used as fungicides, insecticides and anthelmintics.
• R 1 , R 2 and R 3 are the same or different and may be hydrogen or alkyl (for example of 1-6 carbon atoms such as methyl or ethyl), or R 1 and R 2 together or R 2 and R 3 together may form an alkylene chain (for example of 2-5 carbon atoms);
• R 4 is hydroxy, alkoxy (for example of 1-8 carbon atoms such as methoxy or butoxy), substituted alkoxy (for example of 1-8 carbon atoms substituted by halogen or alkoxy such as chloroethoxy or methoxyethoxy), alkenyloxy (for example of 2-4 carbon atoms such as allyloxy), alkylthio (for example of 1-4 carbon atoms such as methylthio or ethylthio), substituted alkenyloxy (for example of 2-4 carbon atoms substituted by halogen such as chloroallyloxy), al
• the present invention is also for a physiological active composition and particularly a herbicidal composition or plant growth composition which contains as an active component a benzofuranyl ester as identified above.
• the physiologically active composition suitably also contains at least one material selected from the group comprising carriers, wetting agents, inert diluents and solvents.
• the present invention is also for the treatment of plants, the soil, land or aquatic areas, or materials which comprises applying thereon or thereto a benzofuranyl ester or a plant physiologically active composition as identified above.
• the substituted benzofuranyl esters according to the present invention generally possess physiological activity. These compounds are useful as herbicides, and also as plant growth regulants. They are also fungicides, insecticides and anthelmintics.
• benzofuranyl esters identified above have been found to be of particular value as selective herbicides for pre-emergence use and also are useful for post-emergence use. With some crops, pre-emergence use is of greater importance. At higher concentrations the compounds may also be used as total weedkillers. At much lower concentrations the compounds may be used as plant growth regulants.
• the present invention is for the benzofuranyl esters of the general formula: ##STR3## wherein R 20 is selected from dialkylamino of 2-4 carbon atoms, piperidino, morpholino, 4-methylpiperazinc, pyrrolidino, hydroxy, alkoxy of 1-4 carbon atoms, alkenyloxy of 2-4 carbon atoms, alkynyloxy of 2-4 carbon atoms, alkoxyalkoxy, of 2-8 carbon atoms, alkylthio of 1-4 carbon atoms, --OCOR 28 , --SO 2 R 29 and --O--O--R 29 , where R 28 is alkyl of 1-4 carbon atoms or phenyl; where R 29 is alkyl of 1-4 carbon atoms; where R 21 is hydrogen or together with R 20 represents an oxygen atom, where R 22 and R 23 represent hydrogen or alkyl of 1-4 carbon atoms; where R 25 represents R 30 SO 2 -- where R 30 is alkyl of 1-4
• the present invention is for the benzofuranyl esters according to the general formula above in which R 1 , R 2 and R 3 are selected from hydrogen and alkyl, or R 1 and R 2 together or R 2 and R 3 together form an alkylene chain; where R 4 is hydroxy, alkoxy, substituted alkoxy, alkenyloxy, alkylthio or --NR 6 R 7 , and wherein R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 have the significance indicated above.
• the present invention is for the benzofuranyl esters according to the general formula above in which R 1 , R 2 and R 3 are selected from hydrogen and alkyl, or R 1 and R 2 together or R 2 and R 3 together form an alkyene chain; where R 4 is --OCOR 13 or --OSO 2 R 14 , and wherein R 5 , R 10 , R 11 , R 12 , R 13 and R 14 have the significance indicated above.
• the present invention is for the benzofuranyl esters according to the general formula above in which R 1 , R 2 and R 3 are selected from hydrogen and alkyl, or R 1 and R 2 together or R 2 and R 3 together form an alkylene chain; where R 4 is the group --O--O--R 15 , or R 3 and R 4 together represent an oxygen atom or the group ⁇ NR 16 ; wherein R 5 , R 8 , R 9 , R 10 , R 11 , R 12 , R 15 and R 16 have the significance indicated above.
• the 5-benzofuranyl esters according to the present invention may be prepared by the reaction between the corresponding 5-hydroxybenzofuran of the formula: ##STR4## and an acylating agent of the formula R 5 X or (R 5 ) 2 O where X is halogen, particularly chlorine.
• the reaction is preferably carried out in the presence of an acid acceptor such as an organic base (for example pyridine or triethylamine) or an alkali (for example an alkali metal carbonate or bicarbonate).
• the benzofuranyl esters where R 4 is the group --OCOR 13 or --OSO 2 R 14 may be prepared by reacting the corresponding compound where R 4 is hydroxy, with a compound of the formula R 13 COX or R 14 SO 2 X (in which X is halogen), the groups R 1 -R 14 having the significance indicated above.
• the compound R 13 COX is an acyl halide and the product is a 2-acyloxybenzofuran; in the case where R 13 is a substituted amino group, the compound R 13 COX is a substituted carbamoylhalide and the product is a 2-carbamoyloxybenzofuran; in the case where R 13 is an alkoxy group or aryloxy group, the compound R 13 COX is a haloformate and the product is a carbonate ester.
• R 13 is an alkylamino group
• the compounds can also be prepared by the reaction between a 2-hydroxybenzofuran of the formula above and an alkyl isocyanate.
• R 13 is a hydrocarbon group
• the compounds can also be prepared by the reaction of a 2-hydroxybenzofuran of the above formula or a corresponding 2-alkoxybenzofuran with an acid anhydride of the formula (R 13 CO) 2 O.
• the benzofuranyl esters where R 4 is the group --O--O--R 15 may be prepared by reacting the corresponding compound where R 4 is hydroxy, with a hydroperoxide of the formula R 15 OOH.
• benzofuranyl esters where R 3 and R 4 together represent the group ⁇ NR 16 may be prepared by reacting a ketenimine with a benzoquinone to form the 2-imino-5-hydroxybenzofuran according to the equation: ##STR5## which is then reacted with a compound of the formula R 5 Cl to give the desired compound.
• the benzofuranyl esters where R 3 and R 4 together represent an oxygen atom may be prepared by the oxidation of the corresponding compound where R 3 is hydrogen and R 4 is hydroxy, alkoxy, --NR 6 R 7 or --OCOR 13 (where R 6 and R 7 are alkyl, substituted alkyl or heterocyclic and R 13 is alkyl, alkenyl or alkynyl, substituted or unsubstituted), for example using chromic oxide in acid, or by the hydrolysis of the corresponding compound in which R 3 and R 4 together represent ⁇ NR 16 .
• the benzofuranyl compounds are generally water insoluble and may be formulated in any of the conventional ways for insoluble compounds.
• benzofuranyl esters may be dissolved in a water immiscible solvent, such as for example a high boiling hydrocarbon, suitably containing dissolved emulsifying agents so as to act as a self-emulsifiable oil on addition to water.
• a water immiscible solvent such as for example a high boiling hydrocarbon, suitably containing dissolved emulsifying agents so as to act as a self-emulsifiable oil on addition to water.
• the benzofuranyl esters may also be admixed with a wetting agent with or without an inert diluent to form a wettable powder which is soluble or dispersible in water, or may be mixed with the inert diluent to form a solid or powdery product.
• Inert diluents with which the benzofuranyl esters may be incorporated include solid inert media comprising powdered or divided solid materials, for example, clays, sands, talc, mica, peat, fertilizers and the like, such products either comprising dust or larger particle size materials such as granules.
• the wetting agents used may comprise anionic compounds such as for example soaps, fatty sulphate esters such as dodecyl sodium sulphate, octadecyl sodium sulphate and cetyl sodium sulphate, fatty aromatic sulphonates such as alkylbenzene sulphonates or butyl naphthalene sulphonate, more complex fatty sulphonates such as the amide condensation product of oleic acid and N-methyl taurine or the sodium sulphonate or dioctyl succinate.
• anionic compounds such as for example soaps, fatty sulphate esters such as dodecyl sodium sulphate, octadecyl sodium sulphate and cetyl sodium sulphate, fatty aromatic sulphonates such as alkylbenzene sulphonates or butyl naphthalene sulphonate, more complex fatty sulphonates such as the amide condensation
• the wetting agents may also comprise non-ionic wetting agents such as for example condensation products of fatty acids, fatty alcohols or fatty substituted phenols with ethylene oxide, or fatty esters and others of sugars or polyhydric alcohols, or the products obtained from the latter by condensation with ethylene oxide, or the products known as block copolymers of ethylene oxide and propylene oxide.
• the wetting agents may also comprise cationic agents such as for example cetyl trimethylammonium bromide and the like.
• physiologically active compositions according to the present invention may contain in addition to the benzofuranyl esters, other physiologically active materials such as herbicides, insecticides, fungicides and molluscicides. It has been found that particular advantages are obtained with mixtures with other herbicides.
• a further embodiment of the present invention is for a herbicidal composition which comprises a mixture of the benzofuranyl esters as identified above and a second herbicide.
• the second herbicide may be for example a phenoxyaliphatic acid, substituted urea, triazine, phenol, nitrile, bipyridylium compound, substituted benzoic acid, halogenated aliphatic acid, carbonate, thiocarbonate, chloroacetanide, diazine, arsenic compound or other herbicidal compound.
• the second herbicide is preferably a substituted phenoxyaliphatic acid; in respect of selective herbicidal compositions for pre-emergence use, the second herbicide is preferably a substituted urea or triazine.
• the phenoxyaliphatic acid generally comprises alkyl and/or halogen substituted phenoxyaliphatic acids, and their salts, for example alkali metal, amine and alkanolamine salts, and functional derivatives, for example esters and amides. These compounds may be of activity such that they are recognised as commercial herbicides, or may be of only slight herbicidal activity.
• substituted phenoxyaliphatic acids examples include 2,4-dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid; 2,4,5-trichlorophenoxyacetic acid, gamma-2,4-dichlorophenoxy-butyric acid, gamma-2-methyl-4-chlorophenoxy-butyric acid, alpha-2-methyl-4-chlorophenoxypropionic acid.
• the substituted urea generally comprises a tri- or tetra-substituted urea such as N'-parachlorophenyl-N,N dimethylurea, N-butyl-N'-(3,4-dichlorophenyl)-N-methylurea, N'-parachlorophenyl-O,N,N-trimethylisourea, N'-p-chlorophenyl-N-methoxy-N-methylurea, N,N-dimethyl-N'-phenylurea.
• a tri- or tetra-substituted urea such as N'-parachlorophenyl-N,N dimethylurea, N-butyl-N'-(3,4-dichlorophenyl)-N-methylurea, N'-parachlorophenyl-O,N,N-trimethylisourea, N'-p-chlorophenyl-N-methoxy-N-methyl
• the triazine herbicide generally comprises a compound of the formula: ##STR6## where X is a halogen, OY group or SY group, where Y is an alkyl group, and R 7 , R 8 , R 9 and R 10 are hydrogen or alkyl, such as 2-chloro-4,6-bisethylamino-1,3,5-triazine or 2-chloro-6-ethylamino-4-isopropylamino-1,3,5-triazine.
• the phenol herbicide generally comprises 4,6-dinitro-o-cresol or pentachlorophenol.
• the nitrile herbicide generally comprises 3,5-diiodo-4-hydroxy-benzonitrile, 3,5-dibromo-4-hydroxybenzo-nitrile or 2,6-dichlorobenzonitrile.
• the bipyridylium herbicide generally comprises 1,1'-dimethyl-4,4'-bipyridylium dichloride or 1,1'-ethylene-2,2'-bipyridylium dibromide.
• the substituted benzoic acid herbicide generally comprises 2,3,6-trichloro-benzoic acid or 2-methoxy-3,6-dichlorobenzoic acid.
• the halogenated aliphatic acid herbicide generally comprises trichloroacetic acid or 2,2-dichloropropionic acid.
• the carbamate herbicide generally comprises isopropyl N-(3-chlorophenyl) carbamate or 4-chloro-2-butynyl N-(3-chlorophenyl) carbamate.
• the thiocarbamate herbicide generally comprises S-ethyl N,N-dipropylthio-carbamate, S-ethyl N,N-diisobutylthiocarbamate and S-(2,3-dichloroallyl) N,N-diisopropylthiocarbamate.
• the chloroacetamide herbicide generally comprise N,N-diallyl-2-chloroacetamide or N-isopropyl-2-chloroacetanilide.
• the diazine herbicide generally comprises 5-bromo-6-methyl-3-sec-butyluracil, 3-cyclohexyl-5,6-trimethyleneuracil or 1,2-dihydropyridazine-3,6-dione.
• the arsenic herbicide generally comprises a salt of methane arsonic acid or cacodylic acid.
• herbicides which may be used in such mixtures include aminotriazole,2,3-dichloro-1,4-naphthoquinone,4-amino-3,5,6-trichloropicolinic acid,2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline,6-chloro-2-trifluoromethylimidazo(4,5-b) pyridine and S,S,S-tributyl phosphorotrithioate.
• a further embodiment of the invention comprises a process for the control of weeds, which comprises the use of a mixture of the benzofuranyl ester as identified and a second herbicide.
• the ratio of the benzofuranyl ester to the second herbicide may vary over a wide range according to the particular compounds involved and the intended use. In general the ratio of benzofuranyl ester to second herbicide lies in the range 1:0.1 to 1:15.
• the rate of application is much lower and may comprise for example 0.5-8 pounds per acre, such as 1-4 pounds per acre.
• esters as fungicides or insecticides for the treatment of plants
• low rates of application will also be used such as 0.25-2 pounds per acre.
• the rate of dilution of the active ingredient in the spray does not appear to be critical and may for example be based on volumes of 5-50 gallons per acre.
• the esters may be used as plant growth regulants in standard ways. They can modify the natural growth characteristics of plants without killing them, and in particular are useful as growth retardants, e.g. of grass. Thus, they can be used on ornamental grass to retard growth so that less frequent mowing is required.
• the materials may be sprayed or dipped in a bath containing the esters.
• the treatment liquor suitably comprises an aqueous or organic solvent solution or suspension of the benzofuranyl ester containing for example 50-10,000 parts per million, and preferably 250-1,000 parts per million, of the benzofuranyl ester.
• benzofuranyl esters according to the present invention have been found of particular value in the control or growth retardation of annual and perennial grasses.
• the benzofuranyl esters may be used for the control of couchgrass in crops such as brassica, potato, sugar beet and cereals such as: maize, or for the control of cyperus in cotton.
• 2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl methanesulphonate (7 parts) was treated with a mixture of acetic anhydride (20 parts) and sulphuric acid (0.6 parts) and left at 50° C. for two hours. The solution was then poured into an excess of ice and sodium bicarbonate. An oil precipitated which solidified and was filtered off and recrystallised from 90% aqueous ethanol to give 2-acetoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl methanesulphonate (6.6 parts), melting point 83°-85° C.
• the compounds listed in the table below were each formulated as an attaclay/sand dust and incorporated in John Innes I potting compost at a rate of 130 or 26 parts per million weight/volume active ingredient to soil (respectively approximately 50 or 10 lbs. active ingredient per acre cultivated to a depth of 2 inches).
• the treated soil samples were placed in anodised aluminium pans, 71/2 ins. long ⁇ 33/4 ins. wide ⁇ 2 ins. deep.
• Seeds of peas (Pisum sativum), mustard (Sinapis alba), linseed (Linum usitatissmum), maize (Zea mays), oats (Avena sativa) and ryegrass (Lolium sp.) were sown in the treated soil, one species per pan, watered and placed in a controlled environment room (temperature 22° C., relative humidity 65-85%, artificial illumination 1200 foot-candles for 14 hours per day) for 21 days. The plants were then visually assessed for any growth regulatory or herbicidal effects, all differences from untreated controls being scored on a scale from 0 to 100 in which 0 signifies no effect and 100 signifies complete suppression. The activities against each species are tabulated below.
• Seeds of peas, mustard, linseed, ryegrass, sugarbeet and oats were sown in anodised aluminum pans, 71/2 inches long ⁇ 33/4 inches wide ⁇ 2 inches deep containing John Innes No. 1 potting compost. They were then watered and placed in a controlled environment room (22° C., 65-85% relative humidity and 14 hours/day artificial illumination at 1200 foot candles). Fourteen days after sowing, the seedlings were sprayed with 50% aqueous acetone solutions of the compounds listed in the table below at rates equivalent to 10 lbs. of active ingredient in 80 gallons per acre.
• Aqueous acetone solutions containing 200 parts per million (ppm.) of the compounds listed in the table below together with 125 ppm. of a wetting agent were sprayed on to the leaves of young potato plants having seven fully expanded leaves, until the plants were completely wetted. After 24 hours, the treated plants were inoculated with sporangia of the disease potato blight (Phytophthora infestans). The plants were then placed in a water saturated atmosphere for 24 hours and then kept in a controlled environment room (Temperature 18° C., relative humidity 80-90%) for five days. At the end of this period, the percentage disease control was measured by comparison with control plants sprayed with a solution of wetting agent alone. Results were as follows:
• a wettable powder formulation was made up by grinding the following ingredients:
• Dyapol PT is the sodium salt of a sulphonated cresol/urea/formaldehyde condensate).
• a wettable powder formulation was made up by grinding the following ingredients:
• Hoe S1/263 contains a mixture of a fatty alcohol/ethylene oxide condensation product and an ethylene oxide/propylene oxide block copolymer).
• benzofuranyl esters according to the invention where R 4 is hydroxy in aqueous alkaline solution form the corresponding open chain compound by opening of the furan ring at the oxygen atom; these derivatives possess similar properties to the benzofuranyl esters and are also embraced in the present invention.
• the derivatives are in the form of a salt of the alkali; the alkali used is preferably an alkali metal hydroxide, and the salt is an alkali metal salt.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Dentistry (AREA)
• Wood Science & Technology (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Agronomy & Crop Science (AREA)
• General Health & Medical Sciences (AREA)
• Pest Control & Pesticides (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Plural Heterocyclic Compounds (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Furan Compounds (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Applications Claiming Priority (6)

Related Parent Applications (1)

Publications (1)

Family

ID=27254919

Family Applications (1)

Country Status (18)

Families Citing this family (5)

Citations (4)

• 1969
  • 1969-05-07 IL IL32186A patent/IL32186A/xx unknown
  • 1969-05-12 LU LU58632D patent/LU58632A1/xx unknown
  • 1969-05-12 IE IE661/69A patent/IE32808B1/xx unknown
  • 1969-05-13 CH CH729269A patent/CH515682A/fr not_active IP Right Cessation
  • 1969-05-13 BE BE733003D patent/BE733003A/xx not_active IP Right Cessation
  • 1969-05-15 CA CA051,608A patent/CA1012539A/en not_active Expired
  • 1969-05-16 ZM ZM71/69A patent/ZM7169A1/xx unknown
  • 1969-05-19 FR FR6916046A patent/FR2009938A1/fr active Pending
  • 1969-05-21 ES ES367496A patent/ES367496A1/es not_active Expired
  • 1969-05-22 AT AT487269A patent/AT300456B/de not_active IP Right Cessation
  • 1969-05-22 DE DE1926139A patent/DE1926139C3/de not_active Expired
  • 1969-05-22 DK DK279069A patent/DK149650C/da not_active IP Right Cessation
  • 1969-05-23 NL NL6907983.A patent/NL163512C/xx not_active IP Right Cessation
  • 1969-05-23 SE SE07348/69A patent/SE366039B/xx unknown
  • 1969-05-23 OA OA53619A patent/OA03064A/xx unknown
  • 1969-05-23 JP JP3967769A patent/JPS5545523B1/ja active Pending
  • 1969-05-23 NO NO2136/69A patent/NO125232B/no unknown
• 1973
  • 1973-03-13 JP JP48028613A patent/JPS5125025B1/ja active Pending
• 1977
  • 1977-06-08 US US05/804,752 patent/US4345932A/en not_active Expired - Lifetime

Patent Citations (4)

Also Published As

Similar Documents

Legal Events